JPH0618821B2 - Preparation and use of catalyst for olefin polymerization - Google Patents

Abstract

A method of producing a polymerization catalyst component suitable for use in the polymerization of alpha-olefins, which method comprises forming an active component by co-comminuting an inorganic Lewis acid, a first organic electron donor, a support base selected from the group consisting of the Group IIA & IIIA salts and the salts of the multivalent metals of the first transition series with the exception of copper, and a polymerization active tri-, tetra-, or pentavalent transition metal compound of a Group IVB-VIB metal, and heating the active component in an inert hydrocarbon solvent to produce the polymerization catalyst component. The active component can be heated in the inert hydrocarbon solvent in the presence of an additional polymerization active tri-, tetra-, or penta- valent transition metal compound of a group IVB-VIB metal. In addition, a second organic electron donor may be incorporated in the active component.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a supported catalyst component for the production of polyolefins and a process for making and using the component.

It has already been made to produce a polymer having a high degree of stereoregularity by using a combination of an organometallic compound and a transition metal compound as a catalyst for producing a high molecular weight polymer from ethylene and α-olefin. .

The base catalyst used in these methods is formed by combining a transition metal salt with a metal alkyl or hydride. Titanium tetrachloride and aluminum alkyls such as triethyl aluminum or diethyl aluminum chloride are often used. However, catalysts of this type are generally less productive and the polymers obtained are less stereoregular.

The isotactic polypropylene is produced by the head-to-tail linkage of the monomer units, whereby
All asymmetric carbon atoms will have the same structure.
The isotactic index is a measure of the percentage of isotactic isomers in the polymer. The atactic polypropylene results from the random attachment of the monomer units. Isotactic polypropylene is a very useful commercial product with high tensile strength, hardness, stiffness, resilience, clarity and excellent surface gloss. Polypropylene is widely used commercially for injection moldings, films, sheets, filaments and fibers. Commercially useful polypropylene essentially contains stereoregular or isotactic isomers.

In most applications, polymers made with these base catalysts are subjected to extraction treatments to increase the percentage of isotactic (stereoregular) polymers in the final product, which is atactic (non-stereoregular). of)
The polymer must be removed. Also, the polymers produced by this method require a deashing treatment to remove catalyst residues. Additional production steps such as polymer extraction and polymer deashing result in significantly higher production costs of polymers produced with these base catalysts.

The first improvements on these catalysts were achieved by using a mixture of titanium trichloride and aluminum trichloride as catalysts and an aluminum alkyl cocatalyst.

Improvements in the modern era have focused their goal on supported catalysts. Many of the early supported catalysts were based on reaction products of surface hydroxyl-containing compounds and transition metal compounds. Examples include transition metal compounds and Mg (O
(H) Cl reaction products with divalent metal hydroxychlorides (UK Patent 1,024,336), reaction products with Mg (OH) ₂ (Belgian Patents 726,832, 728,002 and
735,291), and SiO ₂ , Al ₂ O ₃ , ZrO ₂ , TiO ₂ and Mg.
Reaction products with O (UK Patents 969,761, 969,767
Nos. 916,132 and 1,038,882).

Some new supported catalysts were based on reaction products of magnesium alkoxides and transition metal compounds. Examples include reaction products of transition metal compounds with Mg (OR) ₂ (US Pat. No. 3,644,318 and Belgian patents 737,778, 743,325 and 780,530).

The other supported catalysts were mainly composed of a reaction product of magnesium chloride and a transition metal compound. There is an example of reacting a titanium compound with MgCl ₂ (US Pat. No. 3,642,746 and Belgian patents 755,185, 744,221 and 747,846).
issue).

The addition of certain Lewis bases (electron donors) to the catalyst system has resulted in catalysts with cocatalysts. In some cases, electron donors have been combined with titanium trichloride in the course of catalyst manufacture. Ethers, esters as electron donors,
Amine, ketone and amine aromatic compounds were used.
Although the catalyst containing the cocatalyst improved the polymer's isotactic index, it was generally impossible to produce the polymer in such a quality and quantity that polymer extraction to remove catalyst residues and polymer deashing could be omitted. .

More recently, high yield catalyst components have been disclosed in U.S. Pat. No. 4,149,990, which are sufficiently high in yield to obviate the need for polymer deashing and polymer extraction. The catalyst component disclosed in the patent is magnesium halide-
It was produced by decomposing an electron donor complex with an organoaluminum compound. However, this catalyst was produced in solution and required cleaning of the catalyst.

Various other patents relating to polymerization catalysts utilizing titanium tetrachloride in combination with compounds selected from the group consisting of magnesium halides, especially magnesium chloride, esters, ethers and aluminum halides have been issued during the last few years. It was Examples of these patents are found in U.S. Pat.
No. 4,143,223, 4,242,479, 4,175,171,
No. 3,888,835, No. 4,226,741, No. 4,107,413 and No.
It is No. 4,107,414.

U.S. Pat.No. 4,347,158 discloses, in one preferred embodiment of the invention, a component support comprising an active ingredient consisting of titanium tetrachloride and aluminum trichloride, magnesium chloride, an ether in the form of anisole, and an ester in the form of ethyl benzoate. Disclosed is a catalyst component including a body. The inventor has found that this catalyst is effective in the polymerization of α-olefins, especially in the production of polypropylene. However, the inventor believes that it would be advantageous to be able to improve this catalyst so that the catalytic efficiency of this catalyst is improved and / or the isotactic index and / or the bulk density of the produced polypropylene is improved. is there.

The necessity of impregnating titanium tetrachloride into the catalyst component is apparent from the above-mentioned patent specifications relating to the catalyst component containing titanium tetrachloride. These patents demonstrate that free or unimpregnated titanium tetrachloride, or its complexes, or other titanium compounds derived therefrom, are detrimental to the effective utilization of this type of catalyst component. There is. Therefore, in the preparation of this type of catalyst, care is taken to ensure that all traces of free or non-impregnated titanium compounds or complexes are removed from the catalyst component. Usually, the above treatment is carried out by washing it with an inert hydrocarbon solvent four times or more after formation of the catalyst components, until all traces of chloride have disappeared. If it becomes clear that no chloride remains in the washing solvent, it is a proof that titanium in an unimpregnated form does not remain on the catalyst component, in which case the catalyst component is ready for use.

In accordance with one aspect of the present invention, a method of preparing a polymerization catalyst component suitable for use in the polymerization of α-olefins comprises (a) one or more organic electrons consisting of AlCl ₃ , ester or ether. The donor compound, a supporting base consisting of MgCl ₂ and a titanium tetrahalide compound having polymerization activity are co-micronized, and (b) the obtained active ingredient is added in an inert saturated hydrocarbon solvent at about 40 to about Heating at a temperature of 150 ° C. for about 1 to 24 hours, (c) using a limited amount of hydrocarbon solvent, and substantially avoiding washing the catalyst with the hydrocarbon solvent,
The result is that free or unbound titanium tetrahalide is left in the catalyst obtained.

The inventor has found that the preferred embodiment of the catalyst component of the present invention constitutes a high efficiency catalyst component for olefin, especially α-olefin polymerization. This catalyst component is
Although only used in the production of polypropylene, the inventor has found that this catalyst component would also be useful in the production of satisfactory homopolymers or copolymers from other α-olefins, low molecular weight dienes and ethylene. Sure.

Co-comminution is a term used in the field of catalyst technology which means that the components are ground or powdered at the same time.

In this particular aspect of the invention, a sequential step involved in the formation of the active ingredient, ie, first forming the component support, and then co-milling the component support with the polymerization active transition metal compound. It is believed by the present inventor that the active ingredient is obtained by forming the active ingredient to give a very effective catalyst ingredient. Although it is possible to change the order of addition of the components for forming the component support, when the polymerization active transition metal compound is blended before forming the component support, the catalyst component with poor effectiveness tends to be produced. The inventor considers.

In the present invention, the active ingredient can be heated in an inert hydrocarbon solvent in the presence of an additional amount of titanium tetrahalide compound having polymerization activity.

In this way, an additional amount of the polymerization active transition metal compound can be added to the catalyst component. The reaction product of this additional amount of the polymerization active transition metal compound, or a complex of this compound with, for example, one or more donors present in the system, is within the solid portion of the catalyst component itself. To the catalyst component slurry, or to the catalyst component liquid portion, or to the catalyst component slurry by adding a portion to the solid portion and a liquid portion to the catalyst component slurry. be able to.

In the present specification, when it is defined that a certain component is incorporated into the catalyst component of the present invention, the range of the components of this type includes the essential components of the catalyst component in the formation of the catalyst component of the present invention. It is to be understood that the resulting donor components are included, as well as complexes of such components and the like. Of course, one should not use a donor component that also produces harmful compounds that are difficult to remove effectively from the catalyst component formed in accordance with the present invention.

The method of the present invention preferably comprises the step of incorporating a second organic electron donor.

The second organic electron donor can be co-milled with the component support, with the constituents of the component support, with the active transition metal compound, or after addition of the active transition metal compound.

The first and second electron donors may be the same or different and contain at least one atom consisting of oxygen, sulfur, nitrogen or phosphorus which functions as an electron donor atom. It can be conveniently selected from the group consisting of compounds.

The first and second electron donors are selected from the group consisting of ethers and esters. Thus, in a particularly preferred embodiment of the invention, the first electron donor is an ether in the form of anisole and the second electron donor is an ester in the form of ethyl benzoate (EB).

In the presently preferred method of making the catalyst components of the present invention, the support base is used in anhydrous form. Alternatively, the support base may be co-milled with a suitable dehydrating agent. If a suitable dehydrating agent is used, it does not have to be removed, since the catalytic performance is not adversely affected thereby. Calcium hydride, calcium carbide and silicon tetrahalide can be used as dehydrating agents, with silicon tetrachloride being preferred.

It is then desirable to first co-mill the support base and the inorganic Lewis acid in a mill, preferably a vibrating ball mill.

After that, the first electron donor is added by co-milling to form a component support. Then, after co-milling together with the component support and incorporating the second electron donor, the active transition metal compound is incorporated.

The inert hydrocarbon solvent can be selected from a wide range of inert saturated hydrocarbons. Thus, the solvent may be, for example, an aliphatic hydrocarbon having from about 2 to 9 carbon atoms. In a preferred embodiment of the present invention, the saturated hydrocarbon may contain from about 2 to 7 carbon atoms, so the saturated hydrocarbon solvent is heptane, hexane,
It can be selected from the group consisting of pentane, especially isopentane, butane and ethane.

Alternatively, the inert hydrocarbon solvent may be a cycloalkane having, for example, about 3 to 7 carbon atoms.

When a relatively low boiling point hydrocarbon is used as the inert hydrocarbon solvent, the catalyst component of the present invention is formed under sufficient pressure so that the solvent effectively acts as a liquid phase solvent.

The present inventors consider that catalyst component slurries of this type formed in accordance with the present invention using relatively low boiling solvents may be advantageous in the gas phase polymerization of olefins. In such a polymerization process, the heat of polymerization is suppressed by removing the solvent by evaporation, and the active transition metal dissolved in the solvent is deposited on the solid portion of the catalyst component and is effectively utilized in the polymerization process. It

Although the ratio of solvent used to prepare the catalyst components in accordance with the present invention can be varied within wide limits, the solvent to component ratio is such that at least a suitable wetting condition is obtained to effectively mix the components. Is convenient.

In one embodiment of the invention, the solvent to component ratio may be from about 3: 1 to about 1: 3 by weight.

In the preferred embodiment of the invention, the solvent to component ratio is about 2: 1 to 1: 1 by weight. The solvent to component weight ratio in the presently most preferred embodiment of the invention is about 3: 2.

The Lewis acid in the present invention is aluminum trichloride.

The supporting base is magnesium chloride.

The support base is preferably a magnesium or manganese salt, most preferably a magnesium halide such as magnesium chloride. The preferred active transition metal compound is titanium tetrahalide, especially titanium tetrachloride. Active transition metals, preferably tetravalent titanium, are currently considered not to be reduced to the trivalent state in the catalyst component. Rather, it is presently considered that this reduction occurs in situ after addition of the organometallic compound during polymerization.

The compounding ratio of titanium to the polymerization catalyst of the present invention can be varied within a fairly wide range. The inventors have found that the ratio of titanium directly affects the efficiency or productivity of the catalyst (“CE”), the isotactic index (“II”) and the bulk density of the polymer. Therefore, by adjusting the titanium content, the desired balance between productivity, isotacticity and bulk density can be obtained.

In one embodiment of the present invention, the titanium content in the polymerization catalyst of the present invention may be about 2 to about 10 weight percent titanium, as metal, based on the weight of the solid portion of the catalyst component. .

In a preferred embodiment of the invention, the titanium content is about 3 as metal, based on the weight of the solid portion of the catalyst component.
To 6 wt% titanium.

According to the inventor's opinion, at least part of the titanium component should be incorporated into the solid part of the catalyst component and at least part of the titanium component should preferably be dissolved in the liquid part of the catalyst component. is there.

In one aspect of the invention, the titanium content incorporated into the solid portion of the catalyst component comprises at least about 40-60% by total weight of the total titanium content.

In a preferred embodiment of the present invention, the titanium content incorporated into the solid portion of the catalyst component is at least about 70-75% by weight of the total titanium content.

If the heating step or the heating period is too short, the advantages of the present invention cannot be fully exerted. Therefore, the heating step of the present invention should be conducted for a time and temperature suitable to obtain suitable productivity, isotacticity and bulk density during use of the catalyst component. For example, heating the active ingredient in an inert hydrocarbon solvent is about 40 ° -150 ° C.
At a temperature of about 1 to 24 hours.

In a presently preferred embodiment of the invention, about 60 ° -10.
The active ingredient is heated in an inert hydrocarbon solvent at a temperature of 0 ° C. for about 2 to 24 hours.

It will be appreciated that variations in temperature and heating time will also occur with the particular inert hydrocarbon solvent used to carry out the process of the present invention.

Similarly, it will be appreciated that the choice of inert hydrocarbon solvent will make a difference in the effectiveness of the catalyst components. The inventor has discovered that hexane is preferred over n-heptane as the inert hydrocarbon solvent. It is presently believed that hydrocarbon solvents with even lower carbon numbers, such as isopentane, butane, and even ethane, may produce improved catalyst components according to the invention.

The inventor has discovered that the component ratios of the catalyst components of the present invention can vary over a range and that the quality of the catalyst components is affected by the component ratios.

In one embodiment of the invention, for every 8 moles of support base used, up to about 3 moles of Lewis acid, about 0.5 to about 3 moles of the first electron donor, about 0.5 to about 3 moles of the second electron donor. , And about 0.1 to about 5 moles of the active transition metal compound, respectively, can be used to practice the method of the present invention.

In one aspect of the invention, for every 8 moles of support base,
About 0.5 to about 2 moles of Lewis acid, about 1.0 to about 1.5 moles of the first electron donor, about 0.8 to about 2 moles of the second electron donor, and about 0.4 to about 2 moles of the active transition metal compound, respectively. Can be used.

In a preferred embodiment of the present invention, the support base may be MgCl ₂ , the Lewis acid may be AlCl ₃ , the first electron donor may be anisole and the second electron donor may be ethylbenzoate. And the active transition metal compound may be TiCl ₄ .

In a preferred embodiment of this aspect of the invention, the components are in the following ratios: (a) MgCl ₂ -about 8 moles, (b) AlCl ₃ -about 1 mole, (c) anisole-about 1.25 moles, (d) ) ethyl benzoate - about 1.5 moles, and (e) TiCl ₄ - used at about 1.5 moles.

This preferred In another example aspect, each component of the present invention, the following proportions: (a) MgCl ₂ - about 8 moles, (b) AlCl ₃ - about 0.7 mol, (c) anisole - about 1.25 moles , (D) ethylbenzoate-about 1.5 moles, and (e) TiCl ₄ -about 1.5 moles.

In yet another example of this aspect of the invention, each component has the following ratios: (a) MgCl ₂ -about 8 moles, (b) AlCl ₃ -about 1 mole, (c) anisole-about 1.25 moles. , (D) ethylbenzoate-about 1.5 moles, and (e) TiCl ₄ -about 1 mole.

The polymerization catalyst component of the present invention is recovered as a slurry and can be used as it is for the polymerization of α-olefin.

In another aspect of the invention, after the heating step, the inert hydrocarbon solvent is at least partially evaporated to obtain the catalyst component,
It can be used. If desired, the solvent may be completely evaporated after the heating step and the catalyst components may be dried prior to use.

It is recognized that when the polymerization catalyst component of the present invention is used in the form of a slurry without removing the inert hydrocarbon solvent, excess transition metal or titanium contained in the solvent remains in the catalyst component used for polymerization. Will be done.

Similarly, when the inert solvent is partially or completely evaporated, the excess transition metal or titanium contained in the solvent is deposited on the solid portion of the catalyst component. Thus, such excess transition metal or titanium is present on the solid portion of the catalyst during the polymerization of olefins with the catalyst component.

In most prior art catalyst systems using similar types of catalyst components, excess transition metal, especially titanium, remaining on the catalyst was found to have significant detrimental effects during use of the catalyst. Since it was done, great care was taken to remove it altogether. Therefore,
In order to remove any traces of free transition metal or titanium components or complexes not directly impregnated into the catalyst component,
Prior art catalysts required careful cleaning. Therefore, many prior art patents have found that all trace amounts of free or non-impregnated or non-deposited transition metal or titanium components or complexes are washed by washing the catalyst components at least 4 times (and often 7 times or more). It teaches that it should be reliably removed from the ingredients.

Surprisingly and surprisingly, contrary to the teachings of the prior art,
The inventor has discovered that the non-impregnated or free titanium component, compound or complex contained in the catalyst component of the present invention does not adversely affect the performance of the catalyst component of the present invention.
Even more surprisingly, an additional amount of titanium or active transition metal compound, component or complex that can be incorporated into the catalyst component by the method of the present invention is advantageous, and such free or non-impregnated titanium is particularly preferred. The inventor has found that it generally results in a catalyst component that is significantly more effective than similar uncompounded catalyst components.

In another aspect of the invention, after the heating step is completed,
The inert solvent is filtered off to obtain the solid catalyst according to the present invention, α-
It can be used for the polymerization of olefins. It has been found by the present inventor that non-impregnated titanium tetrachloride has no detrimental effect and is generally advantageous, so it is only necessary to remove the inert solvent by filtration and to wash off the residual solid catalyst components. No need.

The catalyst of the present invention can be used in the form of a slurry, or can be used in the form of a solid catalyst component when the inert solvent is evaporated or filtered off. Of course, the amount of inert solvent used should be limited. By limiting the amount of inert hydrocarbon solvent, the rate of catalyst production can be maximized. In addition, it goes without saying that the production cost of the catalyst component is limited due to the limited amount of solvent handled in the process. In addition, it is far cheaper than the operating cost of the method in which the solvent after the treatment has to be removed by evaporation or by filtration. If the solvent had to be filtered out, the cost of refining to reuse the solvent would naturally increase with increasing amount of solvent.

As taught in the prior art, the catalyst components of the present invention provide substantial advantages over catalyst components that require substantial washing to remove free unimpregnated or unbound transition metal or titanium components. The inventor believes that it is possible. If the solid catalyst has to be washed four times or more to remove all traces of free titanium from the catalyst components, equipment for its handling, including purification and recovery after washing, should be provided. Depending on the equipment cost to build, the invested capital will swell 5 to 8 times. In addition, it goes without saying that operating costs will increase several times.

The inventor has found that the components of the active ingredient can be separately combined in separate groups to form a complex which can then be added together and co-milled to form the active ingredient.

Further included in the present invention is a polymerization catalyst component suitable for the polymerization of α-olefins produced by any of the methods described herein.

The invention further provides a support base selected from the group consisting of an inorganic Lewis acid, a first organic electron donor, a salt of Group IIA and IIIA, and a salt of a polyvalent metal of the first transition series excluding copper,
And a catalyst component for polymerization containing a trivalent, tetravalent or pentavalent transition metal compound of the IVB to VIB metals having polymerization activity, which is associated with a non-impregnated polymerization active transition metal compound, component or complex in a significant ratio. Included. This ratio of non-impregnated active component can be associated with the catalyst component by being deposited on the solid portion of the catalyst component and / or included in the liquid portion of the catalyst component.

To produce the polyolefin, the catalyst component of the present invention is used with a suitable cocatalyst. Organometallic cocatalysts should preferably be used as cocatalysts.

The presently preferred organometallic cocatalysts are selected from the group consisting of trialkylaluminums, alkylaluminum halides and alkylaluminum hydrides. The most preferred cocatalyst is triethyl aluminum (TEAL).

The present inventor has found that the addition of another electron donor in the course of the polymerization can increase the yield of the stereoregular polymer. The electron donor may be added before, during, or after the cocatalyst is added, or may be added as a preformed complex with the cocatalyst. It is convenient to select this electron donor from the same group as the electron donor incorporated in the catalyst component. Preferred electron donors are aromatic esters, with methyl p-toluate (MPT) being especially preferred.

The molar ratio of organometallic cocatalyst to titanium-containing catalyst component, preferably the number of moles of triethylaluminum to the number of gram atoms of Ti in the catalyst component of the present invention, can be in the range of up to about 400: 1. For laboratory liquid pool polymerizations, a range of about 150-300: 1 is presently considered preferred, with about 240: 1 being particularly preferred. It is presently considered preferable for continuous manufacturing processes to be in the range of about 30-200: 1. The electron donor is selected from the same group as the electron donor of the catalyst component and may be the same as or different from the latter. Preferred electron donors are aromatic acid esters such as ethyl.
It is selected from anisate, methyl p-toluate (MPT) or ethyl benzoate. The most preferred electron donor is methyl p-toluate (MPT). The preferred molar ratio of the organometallic cocatalyst to the electron donor component, preferably the molar ratio of the triethylaluminum of the present invention to the methyl p-toluate is from about 1.0 to 20.0: 1 and from about 2.0 to about.
Most preferred is 3.5: 1.

Accordingly, the present invention includes a method of making a polymer, particularly polypropylene, by the method described herein, and a polymer made by the method described herein.

The catalyst component of the present invention can be used with standard cocatalysts in standard .alpha.-olefin polymerization processes. Thus, the catalyst can be used, for example, in liquid pools, in inert solvents or in gas phase production processes.

The active ingredient of the present invention in its presently preferred embodiment can be prepared by co-milling the components in an inert atmosphere using a ball mill or a vibrating ball mill. It is preferred to initially load the support base into the mill. It is desirable to load the support base in dewatered form into the mill. However, if the support base contains water that needs to be removed, an appropriate amount of dehydrating agent is first added to the support base and the resulting mixture is added at a temperature of about 0 ° C to about 90 ° C for about 15 ° C. Mill for about 48 minutes. This mixing operation is carried out at a temperature of about 35 ° C. to about 50 ° C. for about 6 hours to about 24 hours, optimally about 1 hour.
It is preferably carried out for 5 hours.

Co-milling may be carried out at temperatures from about 0 ° to 90 ° C, with a preferred mixing temperature of about 15 ° to about 50 ° C. The mixing time may be about 15 minutes to about 48 hours. The preferred mixing time is about 12 to about 20 hours, with about 16 hours being optimal. If the mixing is insufficient, a homogeneous mixture cannot be obtained, and excessive mixing causes agglomeration or the particle size of the catalyst component is remarkably reduced, resulting in polypropylene particles formed from the catalyst component. Directly related to diameter reduction.

In another embodiment, the hydrous support base, dehydrating agent and Lewis acid are charged together in a ball or vibrating mill and co-milled at a temperature of about 0 ° to about 90 ° C for about 15 minutes to about 48 hours. The mixing process is preferably conducted at a temperature of about 15 ° to about 50 ° C. for about 12 to about 20 hours, optimally about 16 hours.

A support base, a Lewis acid and, if used, a first electron donor together with a dehydrating agent are co-milled to enhance the support.
d support). Mixing can be carried out at a temperature of about 0 ° to 90 ° C. for about 30 minutes to about 48 hours. The preferred temperature of mixing for about 1 to about 5 hours is about 15 ° to about 50 ° C, although co-milling is optimally performed for about 3 hours.

An active transition metal compound is added to the reinforced support prepared as described above. While many transition metal compounds having the above formula MO _p (OR) _m X _n-2p-m provide good catalyst components, liquid titanium tetrachloride is preferred as the active compound. Active transition metal compounds of this kind are added to a ball or vibration mill in which they are co-milled with a reinforced support. This mixing is carried out at a temperature of about 0 ° to about 90 ° C for about 15 minutes to about 4 minutes.
It can be done over 8 hours. In order to produce an efficient supported catalyst component, it is desirable to carry out this mixing at a temperature of about 40 ° to about 80 ° C. for about 12 to about 20 hours, optimally about 16 hours.

In another aspect of the invention, a second electron donor that is different or identical to the first electron donor can be co-milled with the reinforcing support prior to the addition of the active transition metal compound. In a preferred embodiment, the ethyl benzoate is co-milled with the toughened support in a ball or vibrating mill at a temperature of about 0 ° to about 90 ° C. for about 15 minutes to about 48 hours prior to the addition of titanium tetrachloride. . However, the preferred mixing process is from about 15 ° to about 5 °.
Mixing at 0 ° C. for about 1 to about 5 hours, optimally about 3 hours.

In yet another aspect of the invention, the second electron donor such as ethyl benzoate and the active transition metal compound such as titanium tetrachloride can be premixed prior to adding the resulting complex to the reinforced support. The mixing of this complex with the reinforced support is carried out under the conditions and times described above for the active transition metal compound.

The following examples illustrate specific aspects of the invention. These examples are provided to illustrate aspects of the invention and are not intended to limit the invention.

In these examples, the abbreviations using words and numbers refer to the particular active ingredient and the particular catalyst ingredient according to the invention. These abbreviations have the following meanings: (a) Grade 700 catalyst-this refers to the catalyst component according to one preferred embodiment of the invention disclosed in US Pat. No. 4,347,158. Grade 700 catalyst components are formed by co-milling certain components in a ball mill. These components have the following molar ratios: MgCl ₂ 8; AlCl ₃ 1.5; anisole 1.2.
5; ethyl benzoate 1.5; used with TiCl ₄ 0.51−.

(b) Grade 700 modified catalyst - This modifies the grade 700 catalyst component is obtained by changing the molar ratio of AlCl ₃ from 1.5 1.0.

(c) Grade 750 catalyst-This is a Grade 7 catalyst which is formed into the catalytic component of the present invention by heating in the presence of an inert hydrocarbon solvent in the form of hexane.
00 catalyst.

(d) Grade 751 catalyst-this is Grade 7 with the active ingredient formed on the catalyst component of the present invention by heating in the presence of an inert hydrocarbon solvent in the form of heptane.
00 catalyst.

(e) Grade 752 catalyst-this is mineral oil (Exxon)
PRIMO L-355] produced by heating in the presence of an inert hydrocarbon solvent to form the catalyst component of the present invention.

(f) Grade 750 modified catalyst-this means a Grade 700 modified catalyst which has as its active ingredient the catalyst component of the invention formed by heating in the presence of an inert hydrocarbon solvent in the form of hexane. .

(g) Grade 751 modified catalyst-this means a Grade 700 modified catalyst whose active ingredient is the one formed in the catalyst component of the invention by heating in the presence of an inert hydrocarbon solvent in the form of heptane. .

(h) Grade 760 catalyst--this is the active component formed by heating in the presence of an inert hydrocarbon solvent in the form of hexane with TiCl ₄ further incorporated into the solvent to form the catalyst component of the present invention. Means grade 700 catalyst.

(i) Grade 761 catalyst-this is the active component formed by heating in the presence of an inert hydrocarbon solvent in the form of heptane with TiCl ₄ further incorporated into the solvent to form the catalyst component of the present invention. Means grade 700 catalyst.

(j) Grade 760 modified catalyst-this is more TiC in solvent
by heating in the presence of an inert hydrocarbon solvent l ₄ in the form of hexane was incorporation means Grade 700 modified catalyst for the one formed in the catalyst component of the present invention as an active ingredient.

(k) Grade 761 modified catalyst-this is more TiC in solvent
by heating in the presence of an inert hydrocarbon solvent in the form of a hexane plus l _4, it means a grade 700 modified catalyst for the one formed in the catalyst component of the present invention as an active ingredient.

Example I (Control) Preparation of Standard Grade 700 Catalyst 10 mg anhydrous MgCl ₂ and 656 g anhydrous AlCl ₃
In a vibrating mill, the mixture was milled at 30 ° C. for 16 hours to produce a standard grade 700 catalyst. Then 44
0 g of anisole was added to the mill over 30 minutes and the mixture was milled at 30 ° C. for a total of 3 hours. Then 739 g of ethyl benzoate was added to the mill over 30 minutes and another 30
Milling was continued for a total of 3 hours at ° C. Finally, 310 g of TiCl
₄ was added to the mill over 30 minutes and milling was continued at 30 ° C. for an additional 8 hours. A standard grade 700 catalyst was thus obtained, the molar ratio of the components used was MgCl ₂ 8; AlCl ₃
1.5; anisole 1.25; ethyl benzoate 1.5; and T
It was iCl ₄ 0.51.

This Grade 700 catalyst represents one preferred embodiment of the catalyst disclosed in US Pat. No. 4,347,158. In some of the examples described below, this grade 70 was used as the active ingredient to form the catalyst component of the present invention.
0 catalyst was used.

Example II Preparation of Standard Grade 700 Modified Catalyst Except that the AlCl ₃ molar ratio was changed from 1.5 to 1.0 and the ethylbenzoate was added prior to the anisole.
The Grade 700 modified catalyst was prepared exactly as for the Grade 700 catalyst prepared in Example I.

Example III Preparation of Grade 751 Catalyst Using the standard grade 700 catalyst prepared according to Example I,
Grade 751 catalyst was prepared according to one embodiment of the present invention. In a 500 ml degassing flask equipped with a mechanical stirrer was charged 100 g of the grade 700 catalyst prepared in Example I. 100 g of n-heptane was added thereto and the mixture was stirred at 95 ° C. for 20 hours. After the heating was stopped, the mixture was stirred for another 0.5 hour until it reached room temperature. In this way a grade 751 catalyst was obtained.

Example IV Preparation of Grade 761 Catalyst A Grade 761 catalyst according to the present invention was prepared using the Grade 700 catalyst of Example I as the active ingredient. In a 500 ml deaeration flask equipped with a mechanical stirrer was charged 100 g of the Grade 700 catalyst of Example I. Grade was added n- heptane 100g containing 0.5 mol of TiCl ₄ per MgCl ₂ each 8 moles contained in 700 in the catalyst. The mixture was stirred at 95 ° C. for 20 hours then brought to room temperature with stirring. This provided the grade 761 catalyst component in the form of a slurry.

Example V Polymerization of Propylene with Grade 700, Grade 751 and Grade 761 Catalysts of Examples I, III and IV 1 volume autoclave (nitrogen flushed and purged)
With 2.1 mmol Et ₃ Al (TEAL) (25% by weight in heptane), then 0.59 mmol methyl p-toluate (MPT).
(0.4 M in heptane) and 14 or 20 mg of one of the catalysts of Example I, Example III or Example IV were charged. In each case, 675 ml of hydrogen were metered into the autoclave under standard temperature and pressure and then 700 mol of liquid propylene were added. In each case, the mixture was heated to 70 ° C. and reacted for 1 hour. After this period, the unpolymerized monomer was evacuated and removed, and the polymer was dried and weighed. The results of the polymerization experiments carried out with the catalyst components of Examples I, III and IV are shown in Table 1 below: Table 1 above shows the results for the Example 700 compared to the Grade 700 catalyst.
It shows that the grade 751 catalyst prepared in III showed a slightly reduced productivity. However, the 751 catalyst exhibited improved isotacticity and substantially improved polymer bulk density. Example IV grade 761
In terms of catalyst, this catalyst exhibited improved productivity, substantially improved isotacticity and substantially improved polymer bulk density as compared to the Grade 700 catalyst. Considering that the grade 761 catalyst was incorporated with additional titanium tetrachloride and was used without repeated washing, which was taught by the prior art to be absolutely necessary, grade 700 The substantially improved isotactic index of the grade 761 catalyst compared to the catalyst and its improved bulk density and productivity are particularly surprising.

Example VI Effect of Filtration and Hydrocarbon Washing on Grade 751 Catalyst To investigate the effect of filtration and hydrocarbon washing on Grade 751 catalyst, a grade 751 catalyst was prepared substantially in the same manner as in Example III. That is, using a grade 700 catalyst as an active ingredient, the mixture was slurried in n-heptane and then stirred at 90 ° to 95 ° C for 6 hours.
This catalyst component was used as a grade 751 slurry to test its performance. Further, using a part of the grade 751 slurry, decanting this slurry,
By thoroughly washing with n-heptane and filtering,
A grade 751 solid catalyst component was prepared. Next, the performance of the grade 751 solid content as the catalyst component for polymerization was compared with the performance of the grade 751 slurry as the catalyst component.

The results of the comparisons are shown in the following Table 2 A and B: From Table 2 A and B above, grade 751 in solid form
It can be seen that the grade 751 catalysts in the form of slurries tend to perform better in both productivity and isotacticity, and also substantially better in polymer bulk density than the catalysts. This is contrary to the teachings of the prior art that the improved catalyst from the grade 751 slurry "contaminated" with non-impregnated titanium compound compared to the catalyst component which was thoroughly washed to remove any free titanium compound. It supports the surprising result that the ingredients are obtained. If the teachings of the prior art were followed, the performance results shown in Table 2B above would be substantially better than the performance results shown in Table 2A above. .

Example VII Evaluation of the Effect of Filtration and Hydrocarbon Washing on the Performance of Grade 761 Catalysts To determine the effect of filtration and hydrocarbon washing on the performance of Grade 761 catalysts, a grade 761 catalyst component was prepared in the same manner as Example IV. , An experiment similar to Example VI was performed.

Slurry the Grade 700 catalyst (of Example I) in n-heptane in the presence of an additional amount of TiCl ₄ at 90 ° -95 ° C. for 6 hours, and grade 761 in a manner very similar to Example IV.
The catalyst component was prepared.

Sufficient TiCl ₄ so that the final titanium content in the catalyst slurry is 5.36% of the solid catalyst content as titanium metal.
Was added in n-heptane. Analysis of the above-prepared liquid of the slurry revealed that 4.03% of the titanium of 5.36% as this metallic titanium was impregnated in the solid portion of the catalyst component,
On the other hand, the remaining 1.32% was found to be dissolved in the liquid portion of the catalyst component. The grade 761 catalyst slurry was divided into separate parts. One portion was used as a grade 761 catalyst slurry component for propylene polymerization. For the other portion, it was converted to grade 761 catalyst solids by decanting the slurry, washing with heptane and filtering. By using this grade 761 catalyst solid content as a catalyst component,
Polymerization of propylene was performed and the performance was compared with a grade 761 catalyst slurry. The performance results are shown in Table 3 below.

From Table 3 above, the solid component is slightly superior to the slurry component in isotacticity, but the slurry component is significantly superior to the solid component in bulk density and productivity. Recognize. The presence of the titanium compound, component or complex in the unimpregnated state in the liquid portion of the catalyst component is not detrimental, but rather results in improved bulk density and productivity and is substantially comparable to isotactic titanium. This also supports the surprising result of keeping ticness. Therefore, it was once again demonstrated that the catalyst according to the present invention yields unexpected results.

Example VIII Comparison of Catalysts Made Using Grade 700 and Grade 700 Modified Catalyst Formulations Compare the performance of catalyst components according to the invention prepared using Grade 700 catalyst as the active ingredient and then Grade 700 modified catalyst as the active ingredient. A number of experiments to do this were then performed.

The component molar ratios for the grade 700 catalyst are as follows: MgCl ₂ 8; AlCl ₃ 1.5; anisole 1.25; ethyl benzoate 1.5; and TiCl ₄ 0.51.

The component molar ratios for the grade 700 modified catalyst are as follows: MgCl ₂ 8; AlCl ₃ 1.0; anisole 1.25; ethyl benzoate 1.5; and TiCl ₄ 0.51.

Standard and modified formulation catalyst components according to the present invention were prepared using both standard grade 700 formulation and modified grade 700 modified formulation as active ingredients. In each case, the active ingredient was heated in heptane. Add different amount of additional titanium tetrachloride in heptane for each experiment,
The influence of the variation in the amount of titanium contained in the catalyst component of the present invention was investigated. The titanium content of each catalyst component produced in these experiments is shown in Table 4 below as the% titanium as metallic titanium based solely on the solids content of the individual catalyst components in the form of a slurry.

In the liquid pool experiment, each catalyst component was used as a catalyst component for polymerizing propylene by the method generally shown in Example V. The results of the experiment are shown in Table 4 below. For comparison purposes, the catalysts in the first row of Tables 4A and B below are the starting grade 700 catalysts or grade 70 as comparative examples.
0 correction catalyst.

As is apparent from Tables 4A and 4B, the modified formulation catalyst component has better productivity, isotacticity and polymer bulk density than the standard formulation. It can also be seen from Table 4 that the isotactic index increases with increasing titanium concentration. However, both productivity and polymer bulk density increase and peak with increasing titanium concentration and then begin to decrease.

Contrary to the teachings of the prior art, Table 4 again demonstrates the surprising result of the catalyst component according to the invention that the performance is improved by the addition of non-impregnated titanium.

Example IX The performance of the Grade 700 catalyst is generally an example, using the Grade 750 catalyst, ie, hexane instead of heptane.
The Grade 700 catalyst was compared to that heated in hexane by the method of III. The grade 700 starting catalyst was identified as catalyst number 2235-36-8. Grade 7
50 catalysts with catalyst numbers 2354-10, 2354-20-
6 and 2354-20-14. The results comparing the performance of these two catalysts are shown in the graph of the attached FIG. As is apparent from FIG. 1, standard grade 7 in an inert solvent such as hexane is used in accordance with the present invention.
Heating 00 catalyst results in improved productivity and isotactic index as represented by the difference between the solid line representing the grade 700 starting catalyst and the dashed line representing the grade 750 catalyst of the present invention.

Example X The performance of the grade 700 modified catalyst was compared to the grade 750 modified catalyst component by performing similar experiments.
The results are shown in the attached FIG. It will be seen that there is a more significant difference in productivity and isotactic index between the grade 750 modified catalyst (catalyst number 2327-1W) and the grade 700 modified catalyst (catalyst number 2235-29-8). .

Examples XI and XII Experiments similar to Examples IX and X were conducted to compare the performance of the Grade 700 catalyst with the Grade 751 catalyst component and the performance of the Grade 700 modified catalyst with the Grade 751 modified catalyst component. In other words, examples IX and X
The catalyst components of the invention were prepared in this Example XI and XII using heptane as the inert hydrocarbon solvent instead of the hexane used in. The results of these experiments are shown in FIGS. 3 and 4.

In FIG. 3, line 1 is grade 751 according to the invention.
Catalyst component (Catalyst No. 2354-19-6, 2354-2
6, 2354-44, 2354-45, 2354-4
8), while line 2 represents the grade 700 starting catalyst (catalyst number 917).

In FIG. 4, line 1 is a grade 751 catalyst component (catalyst numbers 2287-37W, 2287-41W, 2327).
-31, 2327-32), while the one-line 2 is a grade 700 modified starting catalyst (catalyst number 2235-28-8,
2235-29-8).

As is clear from FIG. 3 and FIG. 4, the difference in performance between the catalyst component of the present invention and the starting material Grade 700 catalyst or the modified catalyst thereof is smaller than that of FIG. 1 or FIG. Much less. Considering this, hexane seems to be superior to heptane as an inert hydrocarbon solvent in carrying out the present invention.

However, under constant productivity, it will be appreciated that the isotactic index in Figure 4 is greater than in Figure 3. This is probably due to the modification of the formulation by reducing the aluminum trichloride content.

Examples XIII and XIV Further experiments were conducted to compare the effect of changing the type of inert hydrocarbon solvent used to carry out the solvent heating step in the process of the present invention.

In Example XIII, a grade 700 starting catalyst (Catalyst No. 2235-36-8) and a catalyst component of the invention, ie, a grade 700 starting catalyst, obtained by treating it in mineral oil (Primol-335, Exxon). 752 catalyst (catalyst numbers 2327-37, 2354-1, 2354-
4) was compared. The experimental results of Example XIII are shown in FIG.

In Example XIV, the performance of Grade 700 modified catalyst (Catalyst No. 2235-29-8) and the grade formed by heating the Grade 700 modified catalyst in mineral oil (Exxon Primol-335) according to the heating process of the present invention. 752
The performance of the catalyst components (catalyst numbers 2287-24, 2327-6) was compared. The results of these experiments are shown in FIG.

5 and 6, in each case, the starting grade 700 catalyst shown in line 2 is superior in productivity and isotactic index to the grade 752 catalyst or its modified catalyst. You can see that The results of these experiments, shown in Figures 5 and 6, demonstrate that Primol is not a suitable inert hydrocarbon solvent for the process of the present invention. These results also suggest that inert hydrocarbon solvents with a low carbon number tend to be preferable to those with a high carbon number.

Example XV Further experiments were conducted to evaluate the performance of various grade 761 catalysts with varying amounts of titanium.
Grade 761 catalyst is grade 700 as starting material
It was prepared using a catalyst formulation and by heating the formulation in the presence of heptane with various amounts of titanium tetrachloride. The performance of the grade 761 catalysts was compared with each other and also with the performance of the grade 700 modified catalyst.

The results of these experiments are summarized in Table 5 below. In any case, the weight% of titanium in the catalyst refers to the weight% of titanium as metallic titanium contained in the catalyst component, based only on the solid content in the catalyst component.

The results of these experiments are also shown in Figures 7-11.

In FIG. 7, a performance comparison between grade 761 catalyst components having different Ti contents and a performance comparison with a starting grade 700 modified catalyst are made.

The curves in FIG. 7 identified by reference numerals 1 to 6 represent: 1. Starting grade 700 modified catalyst (catalyst no. 2415-
3); 2.Ti2.07% (catalyst number 2354-49); 3.Ti2.28% (catalyst number 2373-3); 4.Ti3.74% (catalyst number 2373-1); 5.Ti5.36 % (Catalyst No. 2373-5); 4.Ti 7.50% (Catalyst No. 2373-12).

Looking at these curves in Figure 7, you will notice that there is a significant gap between curve 1 and curve 2 in terms of productivity and isotactic index. This is considered to be due in part to compression.

From Table 5 and FIG. 7, you can see that as the titanium content increases, the catalytic efficiency and isotactic index increase until they reach the peak, and then start to decrease. Bulk density likewise increases until it peaks,
Then, it begins to decrease, but the decrease phenomenon is not so remarkable as the catalyst efficiency and bulk density.

8-11, the performance of the grade 700 starting correction catalyst (Catalyst No. 2415-3) of FIG. 7 and curve 2 of FIG. 7 (FIG. 8); curve 3 of FIG. 7 (FIG. 9). ); Curve 4 in FIG. 7 (FIG. 10) and curve 5 in FIG. 7 (FIG. 11)
The performance of the grade 761 catalyst formulations, each represented by

Therefore, in each of Figures 8-11, the catalytic efficiency and isotactic index of a particular grade 761 catalyst component is compared to that of the starting grade 700 modified catalyst. Plot data for catalyst efficiency are shown in 8th to 1st.
The data points for the isotactic index are indicated by the circles on the graph in Figure 1, while the data points for the isotactic index are indicated by the circles.

It can be seen from FIGS. 8-11 that both the catalytic efficiency and the isotactic index of the catalyst component according to the invention are superior to the starting grade 700 modified catalyst at all TEAL / MPT molar ratios. Let's do it.

Therefore, the TEAL / MPT molar ratio utilized in the catalyst component according to the present invention can be varied to obtain the desired catalyst efficiency and the desired isotactic index.

From the various experiments carried out as described above, the catalyst component of the present invention prepared by treating the active ingredient in a suitable inert solvent in the presence or absence of an additional amount of the active transition metal compound, It can be seen that it results in substantially improved performance over the active ingredients of the treatment. In particular, when treated in a suitable inert hydrocarbon solvent, the catalyst components of the invention provide improvements in productivity, isotacticity and bulk density.

Experimental results also show that the lower the number of carbon atoms contained in the inert hydrocarbon solvent, the better the performance of the catalyst component of the present invention.

However, the most surprising and unexpected thing is that these experiments left it free in the sense that it remained in the liquid portion of the catalyst component and was not impregnated in the solid portion of the catalyst component. It has been shown that it is advantageous to include an additional amount of active transition metal, including free active transition metal, which can be said to significantly improve the catalytic performance. This is quite contrary to what was taught in the technical department dealing with similar active transition metal compounds. This fact offers the substantial advantage that the cost of repeated treatment of the catalyst component to completely remove and eliminate any traces of the unimpregnated active transition metal compound, component or complex is fully realized.

The catalyst component of the present invention in the form of a slurry can be used as it is or can be stored in that state until the next use. The present inventor has surprisingly found that when the catalyst component is stored in the form of a slurry at room temperature, no remarkable deterioration occurs even after 7 to 8 months. In contrast, when the Grade 700 catalyst was stored at room temperature, it became visible after one month that degradation had occurred.

Experiments conducted as described above show that the catalyst component formulations of the present invention made with the Grade 700 modified catalyst are superior in performance to those made with the Grade 700 catalyst. The present inventors are convinced that if the molar ratio of aluminum trichloride is reduced to less than 1.0 mol, for example 0.7 mol or less, better performance can be expected. Therefore, in the particular application of the invention, the molar ratio of aluminum trichloride should be reduced, for example to 0.7 or preferably to 0.5.
The inventor considers that if the content of aluminum trichloride is reduced to too low a level, the stereospecificity of polypropylene will be significantly reduced. This appears to occur when the molar ratio of aluminum trichloride drops below about 0.5.

The dimensions of the catalyst components of the present invention can be chosen to provide a polymer consisting of the particles of the minimum fine size required.
By adjusting the time of the grinding operation in producing the active ingredient, the particle roughness of the solid catalyst component and thus the particle roughness of the polymer produced can be changed.

Because the catalyst components of the invention can increase productivity, they should show a tendency to reduce catalyst residues in the final polypropylene product. Thus, the need to decalcify the polymer will be eliminated, or at least substantially reduced. The high isotactic index of the polymers obtained by using the catalyst components of the present invention also reduces or eliminates the costly steps of polymer extraction and solvent recovery from polymer manufacturing processes using liquid monomers. Become. Therefore, this leads to significant cost savings.

Furthermore, according to the method of the present invention, it is possible to increase the ratio of the active transition metal compound, and it is not necessary to reduce the excess active transition metal compound or to completely remove the active transition metal compound. You can expect savings. This would not only significantly reduce the cost of building the catalyst component manufacturing plant, but would also reduce operating costs.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph comparing the performance (productivity and isotactic index) of the catalyst component of the present invention and the catalyst component of the prior art performed in Example IX. Figures 4, 5, 6 and 7 are graphs showing similar comparisons made in Examples X, XI, XII, XIII, XIV and XV, respectively, and Figures 8-11 show the prior art in Example XV. 3 is a graph showing the relationship between the catalyst efficiency, the isotactic index, and the TEAL / MPT molar ratio for the catalyst component of 1. FIG. 12 is a flow chart showing the steps for preparing the catalyst component of the present invention. * One or more organic electron donors consisting of esters or ethers. ** In an inert saturated hydrocarbon solvent at 40-150 ° C, 1-
Heat treatment for 24 hours.

 ─────────────────────────────────────────────────── ─── Continued Front Page (56) References Japanese Patent Publication No. 3-27567 (JP, B2)

Claims (33)

[Claims] 1. A process for producing a polymerization catalyst component suitable for use in the polymerization of α- olefins, AlCl _3, 1 or consisting of esters or ethers or more organic electron donor compound, consisting of MgCl ₂ A supporting base and a titanium tetrahalide compound having a polymerization activity are co-finely pulverized, and the obtained active ingredient is heated in an inert saturated hydrocarbon solvent at a temperature of about 40 to 150 ° C. for about 1 to 24 hours. However, at that time, a limited amount of hydrocarbon solvent is used, and
The method as described above, characterized in that the washing of the catalyst with a hydrocarbon solvent is substantially avoided, so that free or unbound titanium tetrahalide is left in the obtained catalyst. 2. A component support is first formed by co-milling a support base which is AlCl ₃ , a first, one or more organic electron donor compounds described above, and MgCl ₂ , and then The method according to claim 1, wherein the active ingredient is formed by co-milling the component support and a titanium tetrahalide compound. 3. A second, one or more organic electron donor compound as described above, which is co-milled to form an active ingredient.
The method according to (1) or (2). 4. The method according to claim 3, wherein the component support or the second organic electron donor together with the component is co-milled. 5. The method according to claim 3, wherein the second organic electron donor is co-milled with a titanium tetrahalide compound. 6. The method according to claim 3, wherein the second organic electron donor is co-milled after the addition of the titanium tetrahalide compound. 7. A method according to claim 3, characterized in that the first electron donor is an ether in the form of anisole and the second electron donor is an ester in the form of ethylbenzoate. The method according to any one of 1) above. 8. An inert saturated hydrocarbon solvent is an aliphatic hydrocarbon having about 2 to 7 carbon atoms, as claimed in any one of claims 1 to 7. The method described in the section. 9. A process according to claim 8, characterized in that the aliphatic hydrocarbon is heptane, hexane, pentane, isopentane, butane, propane or ethane. 10. A solvent-to-ingredient ratio of at least sufficient to provide a wet state suitable for mixing the ingredients, according to any one of claims (1) to (9). The method described in. 11. A process according to claim 10, characterized in that the solvent to component ratio is about 3: 1 to 1: 3 by weight. 12. Process according to claim 11, characterized in that the solvent to component ratio is about 2: 1 to 1: 1 by weight. 13. A process according to claim 12, characterized in that the solvent to component ratio is about 3: 2 by weight. 14. The method according to any one of claims (1) to (13), characterized in that the titanium tetrahalide is TiCl ₄ . 15. A titanium content in titanium tetrachloride of from about 2 to about 10 weight percent titanium as a metal, based on the weight of the solid portion of the catalyst component. The method described in (14). 16. The method according to claim 15, characterized in that the titanium content is about 3 to 6% by weight of titanium as metal, based on the weight of the solid portion of the catalyst component. Method. 17. The method according to claim 1, characterized in that the active ingredient is heated in the presence of an additional titanium tetrahalide compound in an inert aliphatic hydrocarbon solvent. The method according to any one of items. 18. The method according to claim 17, wherein the additional titanium tetrahalide compound is titanium tetrachloride. 19. The method of claim 18 wherein a portion of the titanium component is incorporated into the solid portion of the catalyst component and at least a portion of the titanium component is contained in the liquid portion of the catalyst component. ). 20. The titanium content incorporated within the solid portion of the catalyst component is at least about 40 to 60 of the total titanium content.
%, The method according to claim (19). 21. The titanium content incorporated within the solid portion of the catalyst component is at least about 70 to 75 of the total titanium content.
%, The method according to claim (20). 22. The method according to claim 1, wherein the active ingredient is heated in an inert hydrocarbon solvent for about 6 to 24 hours at a temperature of about 60 ° to 100 ° C.
The method according to any one of (21). 23. Up to about 3 moles of AlCl ₃ , about 0.5 to about 3 moles of the first electron donor, and about 0.5 to about 3 moles of the second electron donor per 8 moles of MgCl ₂ used. body,
And about 0.1 to about 5 moles of the active titanium tetrahalide compound, respectively, are used, the method according to claim (3). 24. About 0.8 mol of MgCl ₂ used per 8 mol.
5 to about 2 moles of AlCl ₃ , about 1.0 to about 1.
Patents characterized by using 5 moles of a first electron donor, about 0.8 to about 2 moles of a second electron donor, and about 0.4 to about 2 moles of an active titanium tetrahalide compound, respectively. The method of claim (23). 25. The method according to claim 23, characterized in that the first electron donor is anisole, the second electron donor is ethyl benzoate, and the active titanium tetrahalide compound is TiCl _4. ) Or (24). 26. The following ratios of the respective constituents: (a) MgCl ₂ -about 8 mol, (b) AlCl ₃ -about 0.5-1.5 mol, (c) Anisole-about 1-1.5. The process according to claim 25, characterized in that it is used in a molar amount of (d) ethylbenzoate-about 1 to 5 mol, and (e) TiCl ₄ -about 0.4 to 2 mol. 27. The following ratios of the respective constituents: (a) MgCl ₂ -about 8 mol, (b) AlCl ₃ -about 1 mol, (c) anisole-about 1.25 mol, (d) ethylbenzoate- Process according to claim 26, characterized in that it is used at about 1.5 mol and (e) TiCl ₄ about 1.5 mol. 28. The following ratios of the respective constituents: (a) MgCl ₂ -about 8 mol, (b) AlCl ₃ -about 0.7 mol, (c) anisole-about 1.25 mol (d) ethylbenzoate. Process according to claim 26, characterized in that it is used at about 1.5 mol and (e) TiCl _{4 at} about 1.5 mol. 29. The following proportions of each constituent: (a) MgCl ₂ -about 8 moles, (b) AlCl ₃ -about 1 mole, (c) Anisole-about 1.25 moles, (d) ethylbenzoate. Process according to claim 26, characterized in that it is used at about 1.5 mol and (e) TiCl _{4 at} about 1 mol. (30) The method according to any one of (1) to (29), wherein the catalyst component for polymerization is recovered as a slurry and used for the polymerization of α-olefin. 31. After the heating step, the inert solvent is at least partially evaporated to obtain a catalyst component, which is used, and the catalyst component is used. The method described in the section. 32. The method according to claim 1, wherein after the heating step, the inert solvent is evaporated and the catalyst component is dried before use. the method of. 33. After the heating step, the inert solvent is filtered off to obtain a solid catalyst component without washing the component,
Using this, claims (1) ~
The method according to any one of (32).